S-triazine derivatives

ABSTRACT

1. AN S-TRAZINE DERIVATIVE OF THE FORMULA   2-((D1-O)2-P(=O)-(CH2)N-O-(3-(R&#34;-O-)-1,4-PHENYLENE)-),4,6-   DI(2-R7,4-R8,R9-PHENYL-)-S-TRIAZINE   WHEREIN D1 REPRESENTS A HYDROGEN ATOM, AN ALKYL RADICAL WITH 1 TO 16 CARBON ATOMS OF THE PHENYL RADICAL, N REPRESENTS AN INTEGER FROM 1 TO 12, R7, R8 EACH REPRESENT A HYDROGEN ATOM, A HYDROXYL RADICAL OR AN ALKYL RADICAL WITH 1 TO 4 CARBON ATOMS, R8 AND R9 ADDITIONALLY EACH REPRESENT A CHLORINE ATOM AND R8 ALSO REPRESENTS THE RADICAL   -O-(CH2)N-P(=O)(-O-D1)2   AND R&#34; REPRESENTS A HYDROGEN ATOM OR THE RADICAL   -(CH2)N-P(=O)(-O-D1)2   WITH D1 AND N HAVING THE ABOVE-MENTIONED MEANINGS.

United States Patent 3,845,049 S-TRIAZINE DERIVATIVES Bernhard Piller,Marly, Switzerland, assignor to Ciba- Geigy AG, Basel, Switzerland NoDrawing. Filed June 14, 1972, Ser. No. 262,855 Claims priority,application Switzerland, June 23, 1971, 9,167/71 Int. Cl. C07d 55/50 US.Cl. 260-248 CS 6 Claims ABSTRACT OF THE DISCLOSURE The present inventionrelates to new s-triazine derivatives. A benzene ring is bound in itsl-position directly to the triazine ring, in its Z-position to anoptionally further substituted hydroxy group and in its 4-position tothe hydrocarbon radical of a phosphonic acid. The s-triazine derivativesare useful to stabilise and protect organic materials, which are damagedby ultraviolet rays.

The present invention relates to new s-triazine derivatives, processesfor their manufacture and the use of these s-triazine derivatives forprotecting organic materials against ultraviolet radiation.

The new s-triazine derivatives correspond to the formula wherein X and Yindependently of one another each denote an unsubstituted or substitutedalkyl radical, an alkenyl, cycloalkyl or aralyl radical or anunsubstituted or substituted monocyclic or bicyclic, aromatic orheterocyclic radical, which is bonded directly or via a divalenthetero-atom grouping to the s-triazine ring, A denotes a hydrocarbonradical, D and D either both denote a hydrogen atom, a cycloalkylradical, an alkenyl radical or an unsubstituted or substituted alkyl orphenyl radical, or one denotes hydrogen and the other denotes acycloalkyl radical, an alkenyl radical or an unsubstituted orsubstituted alkyl or phenyl radical, R denotes a hydrogen atom or thegroup 0 OD l wherein A, D and D have the abovementioned meanings, Zdenotes a halogen atom, an R0 group, wherein R is defined as above, analkyl or alkoxy radical, a phenylalkyl radical or the phenyl radical andp is 0, 1 or 2.

The new s-triazine derivatives are above all suitable for protectingorganic materials, especially photographic materials, againstultraviolet radiation.

Cycloalkyl radicals D and D' preferably contain 5 or 6 ring members.Alkenyl radicals D and D as a rule contain 3 to 24 carbon atoms, whilstthe preferred branched or especially unbranched alkyl radicals D and D'can contain 1 to 26 carbon atoms.

Possible substitutents of alkyl radicals X, Y, D and D are, for example,halogen atoms, such as fluorine, chlorine, bromine and iodine, hydroxylgroups, alkoxy groups, such as methoxy, ethoxy, propoxy, isopropoxy,n-butoxy and secondary or tertiary butoxy groups; phenoxy or phenylgroups or nitro, amino or acylamino groups.

Possible monocyclic or bicyclic, aromatic radicals X and Y arenaphthalene, diphenyl or preferably benzene ice radicals. Such radicalscan be substituted by halogen atoms or hydroxyl, alkyl, alkoxy,cycloalkyloxy, phenyl or phenoxy groups, and the alkyl and alkoxy groupscan possess 1 to 24 carbon atoms. The alkyl, alkoxy, phenyl and phenoxygroups can in turn be substituted further, for example by hydroxyl,nitro, amino, acylamino, alkyl, alkoxy or aryl groups, and alkyl oralkoxy groups can contain 1 to 18, preferably 1 to 4, carbon atoms.

Possible substituents of the X and Y radicals are thus also aralkyl oraralkoxy radicals, such as benzyl, phenethyl, benzyloxy or phenethoxyradicals.

Heterocyclic radicals X and Y are preferably monocyclic S-membered or6-membered radicals such as pyridine, furane or thiophene radicals whichcan be substituted further, for example by halogen atoms or hydroxyl,alkyl, alkoxy, cycloalkoxy, phenyl or phenoxy groups.

Possible alkyl and alkoxy radicals Z are those with at most 24,preferably 1 to 8, especially 1 to 4 carbon atoms, and possiblephenylalkyl radicals Z are, for example, benzyl and phenethyl radicals,preferably benzyl radicals. Possible divalent hetero-atom groupingswhich can join the radicals X and Y and the s-triazine ring are, forexample, -O, S- and --NH groupings.

Preferred s-triazine derivatives correspond to the formula wherein A, D,Z and p have the abovementioned meanings, X denotes a monocyclic orbicyclic aromatic radical which is bonded directly or via a divalenthetero-atom grouping to the s-triabine ring, Y denotes a monocyclic orbicyclic, aromatic radical or a monocyclic, heterocyclic radical, bondeddirectly or via a divalent heteroatom grouping to the s-triazine ringand R denotes a hydrogen atom or the radical ii/ AP wherein A and D havethe abovementioned meanings.

s-Triazine derivatives of particular interest are those of the formulawherein A, D, R, Z and p have the abovementioned meanings and X and Yindependently of one another each denote an unsubstituted or substitutedphenyl radical bonded directly or via a -O-, S or --NH-- bridge to thes-triazine ring.

s-Triazine derivatives which have proved particularly suitable are thoseof the formula wherein A, D and R have the abovementioned meanings and Xand Y independently of one another each denote 3 an unsubstituted phenylradical directly bonded to the s-triazine ring or denote a phenylradical substituted by halogen atoms, hydroxyl groups, substituted alkylradiwherein A, D and R have the abovementioned meanings and R to R eachrepresent a hydrogen or halogen atom, a hydroxyl radical, an alkylradical with l to 4 carbon atoms which is unsubstituted or substitutedby halogen atoms, hydroxyl groups or alkoxy groups, or an alkoxy radicalwith 1 to 8 carbon atoms which is unsubstituted or substituted byhalogen atoms, hydroxyl groups or alkoxy groups, and R R R and Radditionally each represent a phenyl or phenoxy radical which isunsubstituted or substituted by halogen atoms, nitro groups or amino,monoalkylamino or dialkylamino or acylamino groups or alkyl or alkoxyradicals with l to 4 carbon atoms or each represent a cycloalkoxyradical with 5 or 6 ring members or the radical wherein A and D have theabovementioned meanings.

Advantageous properties are shown by striazine derivatives of theformula wherein D represents a hydrogen atom, an alkyl radical with l to16 carbon atoms, or the phenyl radical, n represents an integer from 1to 12; R R and R each represent a hydrogen atom, a hydroxyl radical oran alkyl radical with 1 to 4 carbon atoms, R and R additionally eachrepresent a chlorine atom and R also represents the radical and R"represents a hydrogen atom or the radical with D and n having theabovementioned meanings.

4 s-Triazine derivatives which have proved particularly suitable arethose of the formula v11 Rm R'"-0 Rra- Ru wherein n has theabovementioned meaning, D represents an alkyl radical with 1 to 8 carbonatoms, R represents a hydrogen atom, the methyl radical or the hydroxylgroup, R represents a hydrogen atom, the methyl radical or the radical.

0D2 wherein n and D have the abovementioned meanings, R 2 and R eachrepresent a hydrogen atom or the methyl radical, R represents a hydrogenor chlorine atom or the methyl radical and R represents a hydrogen orchlorine atom and R represents a hydrogen atom or the radical with D;and n having the abovementioned meanings, those of the formula OD3 withD and it having the abovementioned meanings, and those of the formulawherein D and R have the abovementioned meanings and m represents aninteger from 2 to 5. s-Triazine derivatives of, for example, theformulae (X) and (XI) are very particularly interesting.

Unless OD and OD, or both OD or both OD; are ester groups, the compoundsof the for mulae (I) to (VI) can not only be in the form of their freeacids, that is to say with H O P end groups, but also in the form ofsalts. Thus, for'example, they can be wholly or partly in the form ofmetal salts, such as alkali metalsalts or alkaline earth metal salts orammonium salts. Ammonium salts can optionally also be N-substituted.

The form in which the compounds of the formula (I) to (V1) are presentdepends greatly on the conditions under which they separate out duringmanufacture, for example on the chosen pH value or on the cation whichis present in the salt used for separating out the product. The acidgroups can thus be in the form of PO H or -PO -cation groups, such as PONHa, P0 Na 'P03K2, POaLiz, PO3(NH4)3, P03Ca OI' Of course, amines andother customary metals can also be present as cations.

Equally, hydroxyl groups present as substituents can be in the form ofalcoholates.

The radical of the formula in the formula (I) is derived, for example,from compounds of the formula E-A-l wherein E denotes a hydroxyl groupor a nucleofugic group which is removed, for example a halogen atom or asulphonate group of the formula wherein E represents an optionallysubstituted alkyl or aryl radical, for example frombromomethanephosphonic acid, 2-fiuoroethanephosphonic acid,2-chloroethanephosphonic acid, 2-bromoethanephosphonic acid,2-iodoethanephosphonic acid, 3-bromopropanephosphonic acid,4-bromobutanephosphonic acid, S-bromopentanephosphonic acid,fi-bromohexanephosphonic acid, 8-bromooctanephosphonic acid,10-bromodecanephosphonic acid, 12-bromododecanephosphonic acid, 16'bromohexadecanephosphonic acid, S-bromo-3-methylpentanephosphonic acid,4-bromo2-butenephosphonic acid,

and 9-hydroxynonanephosphonic acid.

The radical of the formula in the formula (1) is derived, for example,from phosphites of the formula wherein D" has the meaning indicated forD or D, for example from trimethylphosphite, triethylphosphite,tripropylphosphite, tributylphosphite, trihexylphosphite,tribenzylphosphite and triphenylphosphite.

If the radicals D or D in the formula (I) or the radicals D, D' or D" inthe formula (5) represent organic radicals having the indicated meaning,they are derived from compounds of the formulae wherein X, Y, Z and 2have the indicated meanings are derived, for example, from the triazinederivatives indicated in Table I below. Q in Table I corresponds to theradical Radicals of the formula TABLE I OCH:

Same as above.

C Ha

wm MEG Same as above. --0 C Hz- IIIH COCHa CH3 43- CHzCl l TABLE1Continued X Y Q Q 01 Q 0H CH3 E!) Q Q -0 Same as above D0.

-0CH2CH2OCH2CH3 SQ D0.

--OCHzBr S(CH2)3CH; D0.

-NHCH; Do. CH=CH2 Do. --0 0 112-0 H=CH2 -NH-CI Do. (CHzhOCH: N02

D0. -0(CH2)BOCH8 ONH2 Q 0 O --0om1 I OH HO Do. O(CH2)3CH2 -s-o1 H H H 1F H H H H \Q/ \S/- NH(CH2)11CH3 D0.

MANUFACTURE The s-triazine derivatives of the formula (I) can bemanufactured according to various processes which are 65 or inthemselves known. Depending on the nature and quan- (9) 0 tity ratios ofthe starting products and on the reaction {I,-/ conditions, compounds ofthe formula N O-D' O (8) H0 N 0 0-D 70 x-o c- OA n F N N N N O Dl \C/ Zor mixtures thereof are obtained.

1 1 (Al) One such process is characterised, for example, in that aphenol of the formula x-o C H \C/ z n is reacted with an alcohol of theformula wherein X, Y, Z, A, D, D and p have the indicated meanings. Thisreaction is appropriately carried out in the presence of an agent whichsplits off water or of a Lewis acid, such as concentrated sulphuricacid, dicyclohexylcarbodiimide, zinc chloride, tin tetrachloride orboron trifluoride.

(A.2) Instead of an alcohol of the formula (11) it is also possible touse a phosphonate of the formula (12 /A\ 0 in which case an agent whichsplits oil water is superfluous.

(B.l) A further process is characterised in that a compound of theformula is reacted with a sulphuric acid ester of the formula H0: SO--.Ai

wherein A, D and D have the indicated meanings.

(B.2) Conversely, it is also possible to react a compound of the formula(11) with a sulphuric acid ester of the formula (C.l) A further processconsists of reacting a com pound of the formula (10) with a compound ofthe formula ELI-l wherein E" represents a nucleofugic group which issplit off, for example a halogen atom, preferably a bromine atom, or aradical of the formula -SO E', where in E denotes an optionallysubstituted alkyl or aryl radical, for example a radical of the formulaand A, D and D' have the indicated meanings. Compounds of the formula(19) O O-D with a compound of the formula (11).

The reactions according to B. and C. take place according to methodswhich are in themselves known and are advantageously carried out in anorganic solvent, preferably in an organic solvent which is suitable fornucleophilic substitutions, such as acetone, methyl ethyl ketone,acetonitrile, dimethylformamide, dimethylsulphoxide, nitromethane orsulpholane.

In this reaction it may be of advantage to work in the presence ofacid-binding agents such as, for example, alkali hydroxides or alkalicarbonates.

(D) Products of the formula (I), wherein D and D denote hydrogen atoms,can also be obtained if an ester of the formula (I), wherein D and/or Ddo not represent hydrogen atoms but otherwise have the indicatedmeaning, is hydrolysed directly or via the corresponding acid chlorideto give the acid.

This reaction is carried out in an alkaline or, appropriately, in anacid medium, advantageously in the presence of a strong inorganic acidsuch as hydrobromic acid.

The acids of the formula (I) can also be obtained by reduction of estersof the formula (I).

(E) The esters of the formula (I), wherein D and/or D do not represent ahydrogen atom but otherwise have the indicated meaning can also beobtained if a compound of the formula (I), wherein D and/or D representa hydrogen atom, is esterified in the usual manner.

(F) Trans-esterifications of esters of the formula (I) are alsopossible, preferably in the presence of a transesterification catalyst,for example p-toluenesulphonic acid, or an alkali alcoholate, such assodium methylate.

The compounds of the formulae (10) to (21) can also be in the form ofsalts or alcoholates and be employed in this form.

Using the compounds of the formula (I) it is possible, in principle, tostabilise and protect all those organic materials which are damaged inany form, or destroyed, by the influence of ultraviolet rays. Suchdamage through the action of the same cause, namely ultravioletradiation, can have very diverse effects, for example colour change,

change in the mechanical properties (brittleness, crazing, tensilestrength, flexural strength, abrasion resistance, elasticity andageing), the initiation of undesirable chemical reactions (decompositionof sensitive chemical substances, for example medicines, photochemicallyinduced rearrangements, oxidation and the like, for example of oilscontaining unsaturated fatty acids), the initiation of burning symptomsand irritations (for example in the case of human skin) and many others.The use of the s-triazine derivatives defined above for the protectionof polycondensation products and polyaddition products against theaction of ultraviolet is of preferred signilcance. In addition, a wholeseries of the compounds defined above also displays a stabilising eflecttowards the action of oxygen and heat, and antistatic properties,alongside the said ultraviolet protection effect.

The organic materials to be protected can be in the most diverse statesof processing and states of aggregation, whilst their conjointcharacteristic is sensitivity towards ultraviolet radiation.

As low molecular or higher molecular substances for the protection orstabilisation of which the compounds according to the invention can beused, there may for example be mentioned without implying a restrictionthereto: organic natural substances such as are used for pharmaceuticalpurposes (medicaments), UV-sensitive dyestuffs and compounds which asfoodstuffs or in foodstufls are decomposed through exposure to light(unsaturated fatty acids in oils) and the like.

As examples of high molecular organic substances there may be mentioned.

(I) Synthetic organic high molecular materials such as:

(a) Polymerisation products based on organic compounds containing atleast one polymerisable carbon-carbon double bond, that is to say theirhomopolymers or copolymers as well as their after-treatment productssuch as, for example, crosslinking, grafting or degradation products,polymer blends, products obtained by modification of reactive groupingsin the polymer molecule and the like, such as for example, polymersbased on c p-unsaturated carboxylic acids (for example acrylic acidesters, acrylamides and acrylonitrile), on olefine hydrocarbons such as,for example, a-olefines, ethylene, propylene r dienes, that is to say,therefore, also rubbers and rubber-like polymers (also so-called ABSpolymers), and polymers based on vinyl and vinylidene compounds (forexample styrene, vinyl esters, vinyl chlorides and vinyl alcohol), onhalogenated hydrocarbons, on unsaturated aldehydes and ketones, allylcompounds and the like;

(b) Other polymerisation products, such as are obtainable, for example,by ring opening, for example polyamides of the polycaprolactam type, andalso formaldehyde polymers, or polymers which are obtainable boththrough polyaddition and through polycondensation, such as polyethers,polythioethers, polyacetals and thioplasts.

(c) Polycondensation products or pre-condensates based on bifunctionalor polyfunctional compounds possessing groups capable of condensation,their homo-condensation and co-condensation products and after-treatmentproducts, as examples of which there may be mentioned: polyesters[saturated (for example polyethylene terephthalate) or unsaturated (forexample maleic acid/dialcohol polycondensates as well as theircrosslinking products with co-polymerisable vinyl monomers), unbranchedor branched (also based on polyhydric alcohols, such as, for example,alkyd resins)], polyamides (for example hexamethylenediamine adipate),maleate resins, melamine resins, phenolic resins (for example novolacs),aniline resins, furane resins, carbamide resins and also theirprecondensates and products of analogous structure, polycarbonates,silicone resins and others.

(d) Polyaddition products such as polyurethanes (crosslinked andnon-crosslin-ked) and epoxide resins.

(II.) Semi-synthetic organic materials such as, for example, celluloseesters and mixed esters (acetate or propionate), nitrocellulose,cellulose ethers, regenerated cellulose (viscose and cuprammoniumcellulose) or their after-treatment products, or casein plastics.

(IlL) Natural organic materials of animal or vegetable origin, forexample based on cellulose or proteins such as wool, cotton, silk,raffia, jute, hemp, furs and hair, leather, finely divided woodcompositions, natural resins (such as colophony, especially lacquerresins), glues and also rubber, guttapercha, balata and theirafter-treatment and modification products, degradation products andproducts obtainable by modification of reactive groups.

The organic materials in question, especially plastics from the class ofthe polymers of vinyl chloride saturated and unsaturated polyesters,celluloses and polyamides, can be in the most diverse states ofprocessing (raw materials, semi-finished goods or finished goods) andstates of aggregation. They can firstly be in the form of structures ofthe most diverse shape, that is to say therefore, for example,predominantly three-dimensional articles such as profiles, containers orthe most diverse machined articles, chips or granules, and foams;predominantly two-dimensional articles such as coatings, films, lacquersand impregnations or predominantly one-dimensional articles such asfilaments, fibres, flocks, bristles and wires. On the other hand, thesaid materials can also be in unshaped states, in the most diversehomogeneous and inhomogeneous forms of distribution and states ofaggregation, for example as powders, solutions, normal and invertedemulsions (creams), dispersions, latices, sols, gels, putties, waxes,adhesive compositions and filling compositions and the like. 7

Fibre materials can be in the most diverse predominantly non-textileprocessing forms, for example filaments, yarns, fibre fleeces, felts,waddings or flocked structures, or be in the form of woven textilefabrics or textile laminates, knitted fabrics, paper, cardboards and thelike.

The new stabilisers can, for example, also be employed as follows:

(a) In cosmetic preparations, such as perfumes,

coloured and non-coloured soaps and bath additives, skin creams and facecreams, powders, repellents and especially sun oils and sun creams;

(b) mixed with dyestuffs or pigments or as an additive to dyebaths,printing pastes, discharge pastes or resist pastes. Additionally, alsofor the after-treatment of dyeings, prints or discharge prints;

(c) mixed with so-called carriers, antioxidants, other light protectionagents, heat stabilisers or chemical bleaching agents;

(d) mixed with crosslinking agents, finishes such as starch orsynthetically obtainable finishes;

(e) in combination with detergents. The detergents and stabilisers canalso be added separately to the wash baths to be used;

(f) in combination with polymeric carriers (polymerisation,polycondensation of polyaddition products) which contain thestabilisers, optionally alongside other substances, in a dissolved ordispersed form, for example in the case of coating agents, impregnatingagents or binders (solutions, dispersions or emulsions) for textiles,fleeces, paper and leather;

(g) as additives to the most diverse industrial products in order toreduce their speed of ageing, for example as an additive to glues,adhesives, paints and the like.

Where the protective agents to be used according to the invention areintended to be employed for the treatment of textile organic materialsof natural or synthetic origin, for example woven textile fabrics, theycan be applied to the substrate to be protected in any stage of thefinal processing, such as dressing, creaseproof finishing, dyeingprocesses and other finishing by means of fixing processes similar todyeing processes.

The new stabilisers to be used according to the invention are preferablyadded to, or incorporated in, the

materials before or during their shaping. Thus, for example, they can beadded to the compression moulding composition or injection mouldingcomposition during the manufacture of films, sheets, tapes or mouldingsor can be dissolved, dispersed or otherwise finely distributed in thespinning composition before spinning. The protection agents can also beadded to the starting substances, reaction mixtures or intermediateproducts for the manufacture of fully synthetic or semi-syntheticorganic materials, that is to say also before or during the chemicalreaction, for example in the case of a polycondensation (that is to sayalso to pre-condensates), in the case of a polymerisation (that is tosay also to pre-polymers) or in the case of a polyaddition.

An important technological variant of the stabilisers to be usedaccording to the invention is to incorporate these substances into aprotective layer which protects the material located behind it. This canbe done by applying the ultraviolet absorber to the surface layer of afibre or of a multi-dimensional shaped article. This can be achieved,for example, in accordance with a kind of dyeing process, or the activesubstance can be embedded in a polymer (polycondensate or polyadduct)coating in accordance with surface coating methods, which are inthemselves known, for polymeric substances, or the active substance can,in a dissolved form, be allowed to diffuse or swell into the surfacelayer, using a suitable solvent. Another important variant is to embedthe ultraviolet absorber in a self-supporting essentiallytwo-dimensional carrier material, for example a film or the wall of acontainer, in order thereby to keep ultraviolet radiation away from thesubstance behind it (examples: shop windows, transparent packagings andbottles).

It is obvious from the above that in addition to the protection of thesubstrate or of the carrier substance which contains the ultravioletabsorber, the protection of other concomitant substances of thesubstrate, for example dyestuffs, antioxidants, disinfection additives,antistatic agents and other finishes, plasticisers and fillers, issimultaneously also achieved.

Depending on the nature of the substance to be protected or stabilised,on its sensitivity or on the technological form of protection andstabilisation, the requisite amount of stabiliser can vary within widelimits, for example between about 0.01 and 10 percent by weight relativeto the amount of substrate to be protected. For most practicalrequirements, however, amounts of about 0.05 to 2% sufiice.

The process which follows from the above for protecting organicmaterials against the action of ultraviolet radiation and heat thusconsists of homogeneously distributing the compounds defined above inthe organic materials to be protected, incorporating them into thesurface of these materials or covering the materials to be protectedwith a filter layer which contains the compounds indicated.

In particular, an appropriate procedure is to incorporate the compoundsdescribed above, in bulk or in a dissolved or dispersed form, in ahomogeneously distributed manner into the organic materials to beprotected, in amounts of 0.01 to 10, preferably 0.05 to 2.0, percent byweight relative to the amount of the materials to be protected, beforethe final shaping operation.

If it is intended to accumulate the substance to be used according tothe invention in the surface of the substrate to be protected, that isto say, for example, to apply it to a fibre material (fabric), then thiscan advantageously be effected by introducing the substrate to beprotected into a liquor which contains the dissolved or dispersedUV-absorber. Suitable solvents can be, for example, methanol, ethanol,acetone, ethyl acetate, methyl ethyl ketone, cyclohexanol or water.Similarly to the case of dyeing processes, the substrate to be treatedis left for a certain time-in most cases 10 minutes to 24 hours suffice.i r 1 the liquor at 10 to 120 C., during which time the liquor can beagitated. Thereafter the material is rinsed, washed if desired anddried.

It is frequently advisable to employ the above-mentioned lightprotection agents in combination with sterically hindered phenols,esters of thiodipropionic acid or other organic phosphorus compounds.

Above all, however, the compounds of the formula (I) are suitable forprotecting photographic, especially colourphotographic, material againstultraviolet light, and/ or for the absorption of certain ultravioletregions of electromagnetic radiation for photographic purposes.

The colour-photographic material which is stabilised according to theinvention against the action of ultraviolet radiation can be unexposedor exposed image-wise, and partially or completely processed.Preferably, unexposed or imagewise exposed and fixed colour-photographicmaterial is stabilised against ultraviolet radiation. This can becolour-photographic material for the colour transfer process, butpreferably also for the chromogen process or a dye bleach process,especially the silver dye bleach process, or material which has beenprocessed according to one of these processes.

The compounds to be used according to the invention, or mixturesthereof, can be incorporated in any form into the layers containingdyestuffs or dyestuff components or into coloured or colourlessintermediate layers, backing layers and/or covering layers, optionallycontaining further components, of the colour-photographic materials tobe protected.

The compounds to be used according to the invention can be incorporatedinto the photographic materials, or applied to them, both in themanufacture of the colourphotographic material, for example by castinginto the desired layers, and also before, during or after photographicprocessing, for example by application in bulk, by application with theaid of a binder, for example by over-spraying with a protective lacquer,or by diffusing in from a solution, suspension or emulsion.

The following forms of incorporation of the compounds of the formula (I)are possible:

(1) Incorporation into the layer-forming binder, for example in gelatineor other customary layer-forming agents such as photo-lacquers, whichfor example consist, inter alia, of ethylcellulose or acetylcellulose.

(1.1) Molecularly disperse solution in the binder.

(1.2) Distributed in the binder in the form of association compounds.

(1.3) As addition compounds with the binder.

(1.4) Copolymerised with the hinder or a derivative thereof.

(1.5) Reactively linked to the binder, or grafted, as a pre-polymer,onto the layer-forming polymer.

(1.6) Dispersed in a finely divided form in the binder. For this it ispossible to use the customary dispersing processes such as controlledprecipitation from a liquid or dissolved state, grinding oremulsification of a component solution in a liquid which is immisciblewith the binder or the binder solution and subsequent removal of thisliquid by a washing or evaporation process. The known techniques for themanufacture of dispersions are utilised, such as, for example, the useof dispersing agents, the use of protective colloids, dispersingstirrers, continuous flow chambers and the like.

(1.7) Emulsified as a liquid, in a finely divided form, in the binder.

(2) Incorporation into an auxiliary substrate analogously to 1.1-1.7,which is subsequently, in some form, dissolved in the binder,copolymerised with it or reactively linked to it.

Suitable substrates are, for example: Water-soluble polymers based onacrylic acid and vinylpyrrolidone, polyvinyl alcohols, gelativederivatives, such as gelatine modified by reactive linking, for exampleto triazine derivatives; starch, polyamides and polyacrylonitrile;solvents of low volatility such as esters of dicarboxylic 17 acids,diethyl-laurylamide, tricresyl phosphate and the like.

(3) Incorporation into laminates, for example into cellulose triacetate,polyester or polycarbonate, preferably in a molecularly dispersesolution.

The compounds according to the invention are distinguished by extremelyfavourable spectral absorption, good fastness to diffusion, highfastness to light, outstanding protective action against ultravioletradiation, favourable rheological properties in mixtures with gelatineand, especially, exceptional solubility in dibutyl phthalate (compoundsof the formula I, wherein D and D denote an alkyl radical with l to 4carbon atoms).

Compounds of particularly good solubility in dibutyl phthalate aresummarised in Table H below.

TABLE II Solubility in dibutyl phthalate in percent by weight (g./l g.0! mixture) MANUFACTURING EXAMPLES Example 1 3.7 g. of2',4',2",4"-tetrahydroxy-2,4,6-triphenyl-s-triazine, 7.6 g. of5-bromopentane-phosphonic acid diethyl ester and 3.4 g. of potassiumcarbonate in 40 ml. of methyl ethyl ketone are heated to the boil for 8%hours under reflux, whilst stirring. The reaction mixture is poured outonto 150 ml. of ice-water mixture, the resulting yellow oil is twicewashed with water and twice with petroleum ether and is extracted warmwith 100 ml. of acetone, and the 18 solution is freed of a small amountof insoluble matter by filtration, treated with active charcoal andevaporated to dryness.

6.1 g. of product of the formula (101) of Table III are obtained in theform of a light yellow, viscous liquid.

The compounds of the formulae (102) to (108), (111), (113) and (114) areobtained analogously.

Example 2 3.9 g. of the ester of the formula (101) in 30 ml. of 48%strength hydrobromic acid are heated for 4 hours to the boil underreflux and whilst stirring. 100 ml. of water are added and the productis filtered oif and washed with water until neutral.

The crude product thus obtained is dissolved in 50 ml. of water withaddition of the requisite amount of sodium hydroxide solution, and isfractionally precipitated with 35% strength hydrochloric acid.

1.1 g. of acid of the formula (109) are obtained in the form of a yellowpowder of melting point 145 C.

The compound of the formula (110) is obtained analogously.

Example 3 3.7 g. of 2',4',2",4"-tetrahydroxy-2,4,6-triphenyl-s-triazine,13.5 g. of 3-bromopropane-phosphonic acid diethyl ester and 6.8 g. ofpotassium carbonate in 50 m1. of methyl ethyl ketone are heated to theboil in nitrogen, under reflux and whilst stirring, for 16 hours. Thereaction mixture is poured onto 50 ml. of ice-water mixture, thesupernatant water is decanted oil, the resulting yellow oil is washed 3times with water and twice with petroleum ether and dissolved in 50 ml.of warm acetone, and the solution is treated with active charcoal andevaporated to dryness.

1.2 g. of product of the formula (112) of Table III are obtained in theform of a yellow, viscous oil.

TABLE III N RA) 0 0 D N N 0-D Abs. max. Formula in DMF No. X Y p m D Rin (nm.)

101 HO 0 5 CHzCH; H 3004-350 (")/0-D 0(CH2)u-P\ 102 Same as above QC} 03 OH: H 2984-347 103 do Q 0 3 CHzCH: H 3004-350 104 fln C1 0 3 CHzCH] H2984-345 m (in o a (camera H 29s+a45 106 do Same as above 0 3 CH; H2984-350 107 do "Gal 0 5 OHzOHa H 300+350 108 do 0 5 (CH2)aCHa H 300+3 01m 7 do Sameasabove.-.;: 0 5 H H 2994-352 1 (in o 5 H H aoo+a5a 111...do Sameasabove 0 5 (CHmOH; H 2984-346 TABLE III-Continued Formula E fiio. X Y p m D R in (nm.)

112 d O 3 CHzCH; OCzH 294+338 Q -CaH =0 OCzHs 113 do Same as above 0 12CHzCH; H 305-1-347 114 CH3 CH 0 3 CH CH: H 288+335 s1... 115 H0 0 0 D C10 3 CHzCHx H 3004-349 -0(CHz)mi Ol USE EXAMPLES Example 4 A paste of 100parts of polyvinyl chloride, 59 parts by volume of dioctyl phthalate and0.2 part of the compound of the formula (101) is milled on a calender at145 to 150 C. to give an approximately 0.5 mm. thick sheet. Thepolyvinyl chloride sheet thus obtained absorbs from 280 to 380 nm. inthe ultraviolet region.

After exposure to light in the Fadeometer, no yellowing is yetdetectable after 1,000 hours.

Instead of the compound of the formula (101), one of the compounds ofthe formulae (102) to (108), (111) or (112) to (115) can be used wthequally good success.

Example 5 A mixture of 100 parts of polypropylene and 0.2 part of one ofthe compounds of the formulae (101) or (103) is converted into a hide ona calender at 170 C. This hide is pressed at 230 to 240 C. and a maximumpressure of 40 kg./crn. to give a 1 mm. thick sheet.

The sheets thus obtained are practically opaque to ultraviolet light inthe region from 280 to 380 nm.

After an exposure in the Fadeometer for 500 hours, no reduction in themechanical strength is observed.

Example 6 0.2 part of the compound of the formula (101) are dissolved in1.8 parts of monostyrene and 0.5 part of a cobaltnaphthenate/monostyrene solution (containing 1% of cobalt) is added.Thereafter, 40 parts of an unsaturated polyester resin based on phthalicacid/maleic acid/ ethylene glycol in monostyrene are added and thewho-1e is stirred for 10 minutes. After dropwise addition of 1.7 partsof a catalyst solution (methyl ethyl ketone peroxide in dimethylphthalate), the well-mixed air-free composition is poured out betweentwo glass plates. After about minutes, the 1 mm. thick polyester sheethas solidified to the point that it can be removed from the mould. It isopaque to UV light in the region from 280 to 370 nm. and shows noyellowing after 1,000 hours exposure in the Xenotest.

Instead of the compound of the formula (101) a compound of the formulae(102) to (108), (111) or (112) to (115) can also be used.

Example 7 g. of distilled monostyrene are pre-polymerised in a closedbottle in a heating cabinet at 90 C. for 2 days. 0.25 g. of a compoundof the formulae (101) or (103) and 0.025 g. of benzoyl peroxide are thenslowly stirred into the viscous mass. Thereafter, the mixture is pouredinto a cube-shaped mould of aluminium foil and kept at 70 C. for 1 day.After complete solidification and cooling of the mass, the mould isbroken apart. The block thus obtained is subsequently pressed in ahydraulic press at a temperature of 138 C. and a pressure of 150 kg./cm. to give a 1 mm. thick sheet.

The polystyrene sheets thus manufactured are opaque to UV light in theregion from 280 to 380 nm. On exposure in the Fadeometer, a distinctimprovement in the stability to light is observable, in that polystyrenesheets which contain compounds of the abovementioned formulae show noyellowing on an exposure of 200 hours, whilst sheets without theseadditives have already yellowed.

Example 8 0.1 g. of a compound of the formulae (101) or (103) isdissolved in 40 g. of clear nitro lacquer (25% strength). The lacquer isthen uniformly applied, with a coating knife, to sheets of maple wood,and is completely dry after a short time. The addition of theabovementioned ultraviolet absorbers to the lacquer does not change thecolour shade of the wood. The light colour shade of the lacquered woodremains unchanged even after several days exposure under a UV lampprovided the lacquer contains the above compounds in a concentration ofabout 1%. Untreated wood already darkens after a few days under theexposure conditions indicated.

Similar results are obtained when using acrylic resin or alkyd-melamineresin lacquers.

Example 9 10,000 parts of a polyamide in chip form, manufactured fromcaprolactarn in a known manner, are mixed with 30 parts of the compoundsof the formulae (101) or (103) in a tumbler vessel for 12 hours. Thechips treated in this way are fused in a kettle heated to 300 C. afterdisplacing the atmospheric oxygen by superheated steam and the melt isstirred for half an hour. Thereafter it is extruded under nitrogen of 5atmospheres gauge pressure through a spinneret and the filament spun inthis way and cooled is wound up on a spinning bobbin, which at the sametime causes stretching.

As a result of the addition of the above compounds, the degredation ofthe macromolecules caused on exposure in the Fadeometer and determinedby measurement of the relative viscosity in concentrated sulphuric acidis substantially repressed.

Other compounds listed in the table also behave similarly.

Example 10 g. of compound of the formula (101) are dissolved in g. ofdibutyl phthalate on a water bath. This solution is subsequentlydispersed and diluted, by means of a colloid mill, in a mixture of 200g. of an aqueous 8% strength solution of sodiumalkylnaphthalenesulphanate and 1,600 g. of a 12.5% strength gelatinesolution.

The dispersion is subsequently cast on a transparent cellulosetriacetate strip in such a way that after drying the film produced inthis way has optical density of 1.5 for light of 350 nm. wave e gth.

G. Ammonium thiosulphate 200 Sodium sulphite 15 Sodium acetatetrihydrate 25 Glacial acetic acid 13 Water to make up to 1,000 ml.

After soaking for 2 minutes, the strip is treated for 6 minutes with asolution of the following composition:

37% strength hydrochloric acid ml 70 Potassium bromide g 50 Thiourea 280 2-Amino-3-hydroxyphenazine mg Water to make up to ml. 1,000

Thereafter the strip is soaked for 2 minutes and is subsequentlyimmersed in a silver bleach bath of the following composition:

G. Potassium ferricyanide 75 Potassium bromide 15 Primary sodiumphosphate monohydrate 10 Sodium acetate trihydrate 5 Glacial aceticacid, 10 ml.

Water to make up to 1,000 ml.

Example 11 3.3 ml. of 6% strength aqueous gelatine solution, 2.0 ml. ofa 1% strength aqueous solution of the hardener of the formula and 0.9m1. of a 1% strength solution of the product of the formula (109) arepipetted into a test tube and made up to 10.0 ml. with deionised water.

This solution is vigorously mixed and kept for 5 minutes at 40 C. in awater bath.

The casting solution, at 40 C., is cast onto a 13 cm. x 18 cm.substrated glass plate. After solidification at 10 C., the plate isdried in a drying cabinet with circulating air at 32 C. The opticaldensity of the filter thus manufactured is 1.0 for light of 350 nm.wavelength.

On treatment in photographic processing baths, the optical densityremains unchanged. A similar result is obtained when using the compoundof the formula (110).

Example 12 12 mg. of the compound of the formula (107) are mixed with6.6 ml. of 6% strength aqueous gelatine solution whilst being treatedwith an ultrasonic instrument. 1.0 ml. of a 1% strength aqueous solutionof the hardener of the formula (201) is added and the mixture is made upto 10.0 ml. with deionised water.

The mixture is then cast onto a 13 x 18 cm. substrated glass plate, anddried, as indicated in Example 11.

22 An optical density of 1.0 for light of 350 nm. wavelength results,which remains unchanged on treatment according to Example 10.

Instead of the compound of the formula (107), one of the compoundsaccording to the invention of the formulae (101), (108) or (111) canalso be used.

Example 13 A silver bromide emulsion sensitive to red, which containsthe cyan dyestuif of the formula @SOr-HN on I 0 =N N=N- no. s s 0311 cmH C H03 S S 0 H is cast on a transparent carrier.

Strips are cut from the light-sensitive material thus produced and arecoated with a dispersion, described in Examples 10 to 12, of a compoundaccording to the invention from Table III. Only a gelatine solution isapplied to a strip which serves as a comparison sample.

After undergoing the photographic processing method described in Example10, all strips show the same colour density, measured with red light.

The strips are then exposed for 150 hours by means of a Xenon lamp. Acomparison of the optical densities before and after this exposureprovides a measure of the improvement in the fastness to light as aresult of the protective layer applied. The results are summarised inTable IV below.

Instead of the compounds listed in the Table IV, it is also possible touse one of the remaining compounds listed in the Table III.

Similar results are also obtained on using other dyestuffs customary insilver dye bleach photography, colour transfer photography orchromatogenic photography.

TABLE IV Protective With Improvelayer accompound Dmnx. the dyestufiADmux. ment in cording to 01 the (decrease fastness Example formulaBefore After in DE) to light, in No. No. exposure exposure in percentpercent 1 See the following:

ADmn. percent 46% 1 Comparison sample (gelatine without stabilizer);

Example 14 0.2 g. of compound of the formula (104) is dissolved in ml.of a commercially available photographic lacquer, for exampleCiba-Photolacquer. This mixture is applied onto a hardened gelatinelayer located on a carrier and containing the dyestuff of the formula(202) in a maximum density of 1.00, in such a way that the protectivelayer has an optical density of 1.0 at 350 nm. In the case of theCiba-Photolacquer this corresponds to a layer thickness of approx. 20

After 150 hours exposure with a Xenon lamp, the protective action,calculated according to Example 13, in comparison to a lacquer layer notcontaining any stabiliser, is found to be 54%.

Similar results are obtained on using one of the remaining compoundslisted in the Table III, of the formulae (101) to (103), (105) to (108),(111) or (112) to (115).

23 Example 15 Ektachrome daylight transparency material exposed to whitelight and developed in the usual manner is provided with a protectivelayer produced according to Example 10 and containing the compound ofthe formula (101) (test sample). A sample of the same make-up but notcontaining the compfound of the formula (101) serves for comparisonpurposes (blank sample). Thereafter, both samples are exposed to a Xenonlamp for 48 hours. Before and after the exposure, the filter densitiesfor red, green and blue light (R, G and B) are measured with a GretagD-33 Densitometer. The results are listed in Table V.

B: Improvement in fastness to light .-..{g 16 1 Resulting from thecompound of the formula (101), according to the equation:

1 AD in percent of the test sample AD in percent of the blank sampleWhat we claim is: 1. An s-triazine derivative of the formula (VI) R1wherein D represents a hydrogen atom, an alkyl radical with l to 16carbon atoms of the phenyl radical, n represents an integer from 1 to12, R R and R each represent a hydrogen atom, a hydroxyl radical or analkyl radical with 1 to 4 carbon atoms, R and R additionally eachrepresent a chlorine atom and R also represents the radical a and R"represents a hydrogen atom or the radical with D and 11 having theabove-mentioned meanings.

24 2. An s-triazine derivative according to claim 1, of the formulawherein n has the meaning indicated in claim 1, D represents an alkylradical with 1 to 8 carbon atoms, R represents a hydrogen atom, themethyl radical or the hydroxyl group, R represents a hydrogen atom, themethyl radical or the radical with D; and n having the above-mentionedmeanings.

3. An s-triazine derivative according to claim 1, of the formula whereinn has the meaning indicated in claim 1, D represents an alkyl radicalwith 1 to 4 carbon atoms, R and R each represent a hydrogen atom or achlorine atom and R represents a hydrogen atom or the radical with n andD having the above-mentioned meanings.

25 26 4. The s-triazine derivative according to claim 1, of the whereinD represents an alkyl radical with 1 to 4 carbon formula atoms, Rrepresents a hydrogen atom or a chlorine atom (X) and m represents aninteger from 2 to 5.

OH 6. The s-triazine derivative according to claim 5, of the H5Cz0\(|'])/N\ 5 formula t- H 020 N N (XI) 1 -(cm 5o if 1- 115C320 N N O O C2115ll/ O(CH;)5P\

0 02115 1 5. An s-triazine derivative according to claim 1 of theformula HO OH /0 02H; D-O O N a n o erm5r /P(CH2)mO 0 3 O 02H Ds-O N N 0References Cited UNITED STATES PATENTS 3,450,802 6/1969 Taylor 2609463,676,471 7/1972 Eggensperger et a1. 260410.5

1'1" JOHN M. FORD, Primary Examiner UNITED STATES PATENT OFFICE.CERTIFICATE OF CORRECTION ,..,,,..'.L No. 3,845,049 v Dated October 29,1974 Invent z-( It is certified that error a ppears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

claim 3, cam 24, line 51, structure on the right side change C C- lN\Y//N to I Signet! a nd sealed this 7th day of Jahua ryl'975.

(SEAL) Attes't: v HcCOY M. GIBSON JR. c. MARSHALL DANN,

Attesting Office: Commissioner of Patents F ORM PO-IOSO O-69) USCOMM-DC5O376-F'59 U.S, GOViRPgMQNT PRINfING OFFICE: I969 0-3ii-33l UNITEDSTATES PATENT OFFICE CERTIFICATEOF CORRECTION 1mm NU. 3,845,049 DatedOctober 29, 1974 =QINTER'S T M v Inventor-(s) Bernhard Piller It iscertified that error appears inthe aboveidentified patent and that saidLetters Patent are hereby corrected as shown below:

Claim 3, cam 24, line 51, structure on the right side change N Y 1"/\\1Signer! ahd sealed this 7th day of Ja n'ue ryl'975.

(SEAL) Attes't: Y McCOY M. GIBSON JR. c. MARSHALL DANN,

Attesting Officer Commissioner of' Patents F ORM Po-wso (Yo-es)USCOMM-DC 60376-P69 7 .5. GOVEMQMQNT PRINTING OFFICE I), O-lG-JJI

1. AN S-TRAZINE DERIVATIVE OF THE FORMULA